Process for breaking petroleum emulsions employing certain amine-modified thermoplastic phenol-aldehyde resins



Sept. 30, 1958 M. DE GROOTE 2,854,415

PROCESS FOR BREAKING PETROLEUM EMULSIONS EMPLOYING CERTAINAMINE-MODIFIED THERMOPLASTIC PHENOL-ALDEHYDE RESINS Filed Aug. 6. 1954OH OH OH OH J H H H 1 c c c H H H R R R F|G.l

OH OH 0H J H H 1 c c H R R HaC-C-CH: 0H OH 1 c c 1 R R R FIG. 2

OH OH OH OH 1 H H H J c c c H H H R R R H3CCCH3 FIG. 3

OH OH OH 1 H H c c H H H3C-C-CH3 FIG. 4

2,854,415 Patented Sept. 30, 1958 PROCESSFOR BREG PETROLEUM EMUL- SIONSEMPLOYING CERTAIN -MODI- FIESII)NSTHERMOPLASTI PHENOL-ALDEHYDE RE MelvinDe Groote, University City, Mo., assignor to Petrolite Corporation,Wilmington, Del., a corporation of Delaware pplication August 6, 1954,Serial No. 448,173

9 Claims. (Cl- 252344) type that are commonly referred to as cut oil,roilyoil, emulsified oil, etc., and which comprise fine droplets ofnaturally-occurring waters or brines dispersed in a more or lesspermanent state throughoutthe oil which constitutes the continuous phaseof the emulsion.

It also provides an economical and rapid process for separatingemulsions which have been prepared under controlled conditions frommineral oil, such as crude. oil.

and relatively soft Waters or weak brines. Controlled emulsification andsubsequent demulsification under the conditions just mentioned are ofsignificant value in removing impurities particularly inorganic salts,from pipeline oil.

Attention is directed to my co-pending applications,-

Serial Numbers 288,742, through 288,746, inclusive, filed.

May 19, 1952, all now abandoned. The first of said copendingapplications relates to a process of condensing.

certain phenol-aldehyde resins derived from phenols having afunctionality not greater than 2, therein and hereinafter described indetail, with certain basic nonhydroxylated secondary monoamines, alsotherein described in detail, and formaldehyde.

The second application is similar to the first except that themonoamines employed as reactants are hydroxylated instead of beingnonhydroxylated. The third application is similar to the first oneinsofar that nonhydroxylated polyarnines are employed as reactants.

reactants and the last application is concerned with amines having acyclic amidine group in the reactant regardless of whether it ishydroxylated or not.

The present application is differentiated from the aforementioned fiveapplications in that the resin employed instead of being difunctionaltowards formaldehyde is tetrafunctional towards formaldehyde. Statedanother way this invention is concerned with a process of breakingpetroleum emulsions employing a demulsifier including a synthetichydrophile product obtained by condensing certain phenol-aldehyde resinsderived from a mixture of (A) phenols having a functionality not greaterthan two, and (B) a tetra-functional bisphenol, which are hereinafterdescribed in detail, with certain basic secondary amines, alsohereinafter described in detail, and

formaldehyde. The manufacture of oxyalkylation-susceptible, fusible,organic solvent-soluble water-insoluble, low-stage phenol aldehyderesins having an average molecular weight cor- The fourth ap-, plicationis concerned with hydroxylated polyamines as responding to at least 3and not over 6 phenolic nuclei per resin molecule and obtained withoutthe use of a bisphenol have been described in a large number of patentsincluding among others, U. S. 2,499,367, dated March 7, 1950, to DeGroote and Keiser. Similarly oxalkylationsusceptible, fusible, organicsolvent-soluble, water-insoluble phenol aldehyde resin derived byreaction between an aldehyde having but one functional group reactivewith bisphenol and a difunctional bisphenol reactive towards aldehydeshas been described in the U. S. Patent No. 2,564,191, dated July '14,1951.

As far as I am aware there is no suitable description of a phenolaldehyde resin derived from two classes of phenols, one being a phenolof the formula in which R is an aliphatic hydrocarbon radical having atleast 4 and not more than 24 carbon atoms and substituted in the 2,4,6position; the other being a tetrafunctional bisphenol; the ratio of thetwo classes of phenols employed being so as to contribute one bisphenolresidue per resin molecule and particularly as employed in the presentinvention as a reactant; The nature of the condensate as obtained by thepresent manufacturing process is best understood by referring tocomparable products derived from a difunctional resin rather than atetrafunc tional resin. In this instance functionality refers. toreactivity toward formaldehyde or its equivalent.

For purpose of illustration it may be simpler to divert momentarily tothe products described in the five aforementioned co-pendingapplications, Serial Nos. 288,742 through and including 288,746,inclusive and for sake of simplicity to the first one, i. e., Serial No.288,742, in which the amine reactant is a nonhydroxylated monoamine. Forpurpose of simplicity the invention described in said co-pendingapplication, Serial No. 288,742 may be exemplified by an idealizedformula, as follows:

in which R represents a hydrocarbon substituent gen erally having 4 andnot over 18 carbon atoms but most preferably not over 14 carbon atomsand n generally is a small whole number varying from 1 to 4. In theresin structure it is shown as being derived from formaldehyde althoughobviously other aldehydes are equally satisfactory. The amine residue inthe above structure is derived from a basic amine, and usually astrongly basic amine, and may be indicated thus:

RI HN/ in which R represents any appropriate hydrocarbon radical, suchas an alkyl, alicyclic, arylalkyl radical, etc., free from hydroxylradicals. The only limitation is that the radical should not be anegative radical, which considerably reduces the basicity of the amine,such as an aryl radical or an acyl radical. Needless to say, the twooccurrences of R may jointly represent a single divalent radical insteadof two monovalent radicals. This is illustrated by morpholine andpiperidine. The introduction of two such amino radicals into acomparatively small resin molecule, for instance, one having 3 to 6phenolic nuclei as specified, alters the resultant product in a num: berof ways. In the first place, a basic nitrogen atdmQo'f course, adds ahydrophile effect; in the second place, depending on the sizeof theradical R, there may be a counterbalancing hydrophobe effect or one inwhich the hydrophobe elfectmore than counterbalances the'hydrophileeffect of the nitrogen atom. Finally,'in'such cases where R contains oneor more oxygen atoms, another efit'ect is introduced, particularlyanother hydrophile effect.

Such condensates, i. e., the condensates of Serial No. 288,742, areobtained from conventional phenol-aldehyde resins. It is Well known thatone can readily purchase on the open market, or prepare fusible, organicsolventsoluble, water-insoluble resin polymers of a compositionapproximated in an idealized form by the formula R R R In the aboveformula n represents a small wholenumber varying from 1 to 6, 7 or 8, ormore, up to probably .10 to 12 units, particularly when the resin. issubjected to heating under avacuum as described in the literature. Alimited sub-genus is in the instance of low molecular weight polymerswhere the total number of phenol nuclei varies from 3 to 6, i. e., nvaries from l to 4; R represents a hydrocarbon substituent, generally analkyl radical having from 4 to 14 carbon atoms, such as a butyl, amyl,hexyl, decyl or dodecyl radical. Where the divalent bridge radical isshown as being derived from formaldehyde it may, of course, be derivedfrom any other reactive aldehyde having 8 carbon atoms or less.

Reference is now being made to the accompanying drawing in which Figureldepicts a conventional resin of the kind referred to in my co-pendingapplications Serial Nos. 288,742, through' 288,746, dated May 19, 1952.In the drawing R simply denotes an alkyl radical having 4 to 24 carbonatoms and the arrows indicate two points of reactivity towardsformaldehyde. Needless to say, such resins can be obtained from anydifunctional phenol and not necessarily a parasubstituted phenol.

The other figures in the drawing, towit, 2, 3 and 4, depict in a similarmanner resins of the kind herein employed in which one tetrafunctionalbisphenol has entered into the resin structure and again the letter Rhas its prior significance and again the arrows indicate four points ofreactivity. Obviously orthosubstituted phenols could be employed as well'as parasubstituted phenols.

It is obvious that with difunctional resins the most one could combineisone or two moles of asu'itable amine whereas in the use of resinsherein described one could substitute not only one or two but as many asthreenr four and thus obtain products ofanentirely different characterand particularly have"anincr'e'ased hydrophile property in manyinstances.

Reverting again to what'is said' inlthe five copending applicationspreviously referred to, and particularly to Serial No. 288,742,reference is made to the text which describes other products of reactionwhich appear in the cogeneric mixture resulting-from reaction betweenthe resin, the secondary amine and formaldehyde. The reference is asfollows:

In conducting reactions of this kind one does not necessarily obtaina-hundred percent yield. for'obvious reasons. Certain side reactions maytake place. For instance, 2 moles ofamine may combine with one mole ofthe aldehyde or only one mole of the amine may combine with the resinmolecule, or even to a very slight extent, if at all, 2 resin units maycombine without any amine in the reaction product, as indicated in thefollowing formulas:

R! H /R1 NgN\ R1 R1 OH H OH OH H R 0 0 -O-N H H H R R n R OH OH OH 011OH on H H H H H G- c c- -o -0 H H H H H R n R R R B.

When a difunctional resin is replaced by a tetrafunctional resin inlight of what has been said it becomes apparent, and particularly sowhen the amount of formaldehyde and the amount of amineis increased to 3or 4 moles per mol of resin, that a much more complicated and muchdifferent structure results. Furthermore, to the extent that a molecularweight determination or an approximation thereof can be made theindications point to distinctly higher molecular weights than in thecase of difunctional resins. In any event, the condensates so obtainedare diiferent in character and for some purposes particularly afteroxyalkylation with ethylene oxide, propylene oxide, butylene oxide,glycide, or methylglycide are especially efiective for the resolution ofpetroleum emulsions. Indeed, in many instances the ox'yalkylationderivatives are distinctly more effective than the comparable productsderived from condensates in which difunctional resins are used.

For purpose of convenience what is'said hereinafter will be divided intofour parts:

Part 1 is concerned with phenol-aldehyde resins suitable forcondensation;

Part 2 is concerned with suitable secondary amines which can be employedin' conjunction with the resins in the condensation procedure;

Part 3 is concerned with the condensation procedure as such;

Part 4 is concerned with the uses of thecondensates for the resolutionof. petroleum emulsions.

PART 1 This is concerned with the preparation of phenol-aldehyde resinsof the kind previously referred to, i. e., oxyalkylation-susceptible,fusible, organic solvent-soluble, water-insoluble, low-stagephenol-aldehyde resins having an average molecular weight correspondingto at least 3 and not over 6 phenolic nuclei per resin molecule; saidresin being derived by reaction between an aldehyde having not over 8carbon atoms and reactive towards two classes of phenols, one being (A)a phenol of the formula in whichR is an aliphatic hydrocarbonradicalhaving at least 4. and not more than 24 carbonatoms andsubstituted in the 2,4,6 position; the other being (B) a tetra- 1functional bisphenol; the ratio of the two. classes of phenols employedbeing so as to contribute one bisphenol residue per resinrnolecule.

. method employed: for preparation of such resin is identical 'Withthatdescribed in regard to the preparation of resins obtained solelyfrom difunctional phenols as referred to in U. S. Patent No. 2,499,367or resins obtained from difunctional bisphenol-s as described in U. S.Patent No. 2,564,191.

In either event one can prepare the resin with or without the use of acatalyst. The catalyst may be acid or basic. An acid catalyst such assulfonic acid is preferred. In the present instance the difunctionalphenol as differentiated from the bisphenol may have as many as 24 car-By terms diphenol, diphenylol, bisphenol, and dihydroxydiphenyl as usedherein is meant the dihydroxydiphenylmethanes, including the isomers,homologs and bon atoms substituted in either the ortho or para position.For practical purposes those having 4 to 14 carbon atoms in the sidechain are most suitable. There may or may not be ameta-substituentpresent. The ordinary phenols used are butylphenol,amylphenol, hexylphenol, octylphenol, nonylphenol, decylphenol,dodecylphenol, and tetradecylphenol. Generally, these are .parasubstituted phenols andhave nosu-bstituent in the meta position.Substituents may vary in structure as for example,

the butyl group may be secondary or tertiary and the amylgroup may alsobe secondary or tertiary. Such resins can be prepared with or withoutthe use of a solvent, but for most purposes it is preferable to have asolvent present, The aldehyde used may be any aldehyde having not over-8 carbon atoms and particularly formaldehyde, acetalde-' hyde,propionaldehyde or butyraldehyde.

Resins of the kind herein described, i., e., tetrafunctional resinshaving 3 to 6 phenolic nuclei, one of which is a bisphenol nucleus perresin molecule have not been suitably described but the method ofmanufacture used in connection with the preparation of other comparableresins is entirely suitable.

For instance see U. S. Patent No. 2,499,368, dated March 7, 1950, to DeGroote and Keiser. Resins can be made using an acid catalyst or basiccatalyst or a catalyst showing neither acid nor basic properties in theordinary sense, or without any catalyst at all. It is preferable thatthe resins employed be substantially neutral. In other words, ifprepared by using a strong acid 'as a catalyst, such strong acid shouldbe neutralized. Similarly, if a strong base is used as a catalyst it ispreferable that the base be neutralized although I have found.

that sometimes the reactions described involving amines proceeded morerapidly in the presence of a small amount of free base. The amount maybe as small as a 200th of a percent and as much as a few tenths of apercent. Sometimes moderate increase in caustic soda and caustic potashmay be used. However, the most desirable procedure in practically everycase is to have the resin neutral, except for the basi-city of the aminogroups, of the added reactant in the second step.

In preparing resins one does not get a single polymer, i. e., one havingjust 3 units, or just 4 units, or just 5 units, or just 6 units, etc. Itis usually a mixture; for instance one approximating 4 phenolic nucleiwill have some trimer and pentamer present. Thus, the molecular weightmay be such that it corresponds to a fractional value for n as, forexample, 3.5, 4.5, or 5.2.

In the present instance one follows such well-known procedure but makesa mixture of part of the bisphenol with 2, 3, 4, or 5 parts of adifunctional phenol. The difunctional phenol employed may need not benecessarily the same and for that matter one could employ bothortho-substituted and para-substituted phenols. Resinification iscarried along until the usual methods of molecular weight determination.indicates a molecular weight corresponding to 'a combination of thetetrafunctional bisphenol with an. equivalent amount of difun'ctionalphenols, for-instance a molecular weight corresponding to one mole of atetrafunctional phenol and 2 moles ofa dif-unctlonal phenol or a l and 3combination or a 1 and 5 combination.

Bisphenols are well known and the most ocmmon example, and in fact theonly one produced on a large to be understood that they are in the4,4(para,para') positions on the phenyl rings.

In the instant case, however, bisphenols are limited to tetrafunctionalbisphenols and for practical purposes this.

means bisphenols inmost instances in which all four ortho groups are notsubstituted. Examples of such bisphenols are 'the following:

Comparable bisphenols can be obtained using meta cresol as-the initialreactant instead of phenol. A variety of other comparable diphenols arewell-known as for ex-- ample a diphenol of the following formula where Ris a small alkyl group having not over 8 carbon atoms. For practicalpurposes, however, the most satisfactory bisphenol is bisphenol A.Equally satisfactory is bisphenol B which has the following formula Someother comparable bisphenols are available.

At least one and in some instances two meta-substituted methyl radicalsappear. As to other bisphenols some of which are suitable for theinstant purpose, i. e., are tetrafunctional see U. S. Patents Nos.2,482,728, 2,575,558, 2,626,939, 2,530,353.

As to the preparation of resins one can use the procedure as outlined inExample In in aforementioned U. S. Patent No. 2,499,370. One can use anyof the difunctional phenols described in said patent and furthermore onecan use any of the aldehydes employed and also any of the catalyst andany of the solvents. For purpose of convenience, what is saidhereinafter will be limited largely to the use of formaldehydeparticularly the 37% formaldehyde solution and the use of an acidcatalyst along with xylene or similar solvent. Using the same procedureas described in connection with Example In in aforementioned U. S.Patent No. 2,499,370 and using acid as a catalyst based on the weight ofthe reaction mass :1 number of resins were prepared. as described inreaction with anacetone to give a cogenenc mlxturepf Table I and TableII immediately following: blsphenols which appear to be perfectly satlsfactorywhen TABLE I Diamylr Ex. Bis- Amount, Difunctional Amount,naphtha- Amount, Amount,

No. phegrams phenol grams lene sul- Aldehyde grams Solvent .grams n01fonicacid i A 114 p-Tert-amyl 328 6.3 Form. 37% sol--- 203 High boil.arom. pet. 501., l 461 A i o 328 6.2 --.-do d 474 A 328 8.2 604 A 1974.8 356 A 246 5.2 389 A 273 5.1 37s A 328 6 443 A 164 5.3 414 A 164 5.0;256 A 164 3.3 292 A 164 3.4 -303 A 164 6.2 288.5 A 164 7.2 333 A 1647.4 357 A 164 3.3 315 A .do... 164 s. 365 A 76 Para-cresyl 144 3. 6arom. pet. 501. 243 A 76 p-Ter,b-buty1- 200 4.1 300 A 76 Oetyl-phenoL-275 4.9 H 376 B 81. Nonyl-phenol- 295 5.0 396 O o-Tert-amyl 219 6.2 315D 67 .p-Tert-amyLL- 219 4.1 do 299 Bisphenol A is p,p-dihydroxy diphenyldimethyl methane.

Bisphenol B is the comparable derived from ethyl methyl ketone insteadof dimethyl ketone- Bisphenol O is comparable to bisphenol A but derivedfrom meta-cresol instead of phenol. Bisphenol D is o,o-dihydroxydiphenyl methane.

" TABLE II Molal M01 Max. ratio of ratio of temp.

Ex. bisphewater during Hardness Theo.

No. 1101 to out based resinifi- Color (solv. free melee. Remarks (seenote D) diiunct.- on aldecation, 1 basis) weight 2 phenol hyde 1 C. toaldeh.

-4:5 1.02 150 Al n oer black- The 50% solution is asoit solid.

S .4:4. 4 0. 959 (See note A.) 2:3. 3 0. 994 (See note B.) 22:3 0.1906(b1 2.7 moles H4O liber. permole hisphenol.

ac :3:4 1 0. 974 150 Black-purple. Viscosity at O.=226 cps. :5:6 1. o 1155 Black-red Viseosity=16o cps. at 80 0. 1 :6:7 0. 96 150 Black-br0wu1: 1. 8 0.98 .154 Dark purple '5 0.756 146 Dark brown.-. (See note 0.):4. 4. 5 0. 825 do HzO/bisphenol=3.65 moles, reaction time 17.5 hrs.:424. 5 0. 975 145 Dari; amber... HzO/bisphenol=4.4. 14:5 0. 71 149Brown (dark)- HzO/bisphenol=.3.55, reaction-time 17.5 hrs. :4:5 0. 957143 Dark brown-.. HzO/bisphenol=4.77. .425 0.845 0 406'HrO/bisphenol=4.22, reaction time 17.5 hrs. 24:5 0. 977 147 doH1O/bisphenol=0.984.

'5 0. 956 145 Dark amber HaO/bisphen0l=4.77. 5 0.833 158 Dark brown..H2O/bisphen0l=4.17- 8a 5 0. 833 156 0 D0. 19a-.- 1. 0. 85 153 doHzO/bisphen01=4.18. 20a... 1: 5 0.8 Dark amber H2O/blsphenOl=4. 21a---1: 5 0. 8 159 Dark brow-m. Do. 22a--- 1: .5 0. 867 152 A.-- 0 Very hardresin.

Note A-E50% solution is very viscous, but not as much as when ECHO is 5moles. The viscosity of 50% solution at 100 0. =22 cps. was use i NoteBCrossllnkage occurred during dehydration 110110 to phenol ratio 1:1.1)is probably too high.

Note C-HzO/blSphBIl01--3.78 moles. Reaction is very slow. Reaction=25ours. Thinner solu. thanHCHO resin.

Note D-Reaetion time in all examples 2 to 3 hours except where otherwiseindicated.

1 It is quite possible that in a molal ratio of 1, 4 and 5 that not morethan 4 mols of the aldehyde enters into reaction particularly when anacid catalyst is used. For this reason the value of .8 ior example incolumn 3 corresponding to Examples 206 and 210 may still well betheoretical 100% combination.

2 Theoretical molecular weight based on the single structural unit.

3 Viscosity taken as'50% solution in high boiling solvent.

The resins illustrated by Examples 1a through 22a substituted forbisphenol Ain the above examples.

have been prepared usingbisphenol B instead of bis- PART 2 phenol A. Theproducts obtained were substantially 70 identical'except that they seemto show a little higher 1 As noted previously, a variety of secondaryamines oil solubility endless tendency, if any, towards gel free from aP y amino group. m be 1 formation. The same is true where bisphenol Chas These amines fall into five catego as indicated prebeen employed. Amixture of materials consisting of viously.

3,5 xylenol, m-ethyl phenol, m-cresol was subjected to 7 One categoryconsists of strongly basic secondary monoamines. free from hydroxylgroups whose composition may be indicated thus:

in which R represents a monovalent alkyl, alicyclic, arylalkyl radicaland may be heterocyclic in a few instances as in the case of piperidineand a secondary amine derived from furfurylamine by methylation orethylation, or a similar procedure.

Another example of a heterocyclic amine is, of course,

morpholine.

The secondary amines most readily available are, of course, amines suchas dimethylarnine, methylethylamine,

diethylamine, dipropylamine, ethylpropylamine, dibutylamine,diamylamine, dihexylamine, dioctylamine, and dinonylamine. Other aminesinclude bis(l,3-dimethylbutyl) amine. There are, of course, a variety ofprimary amines which can be reacted with an alkylating agent such asdimethyl sulfate, diethyl sulfate, an alkyl bromide, an ester ofsulfonic acid, etc., to produce suit ableamines within the hereinspecified limitations. For example, one can methylatealphamethylbenzylamine, or

benzylamine itself, to produce a suitable reactant. Needless to say, onecan use secondary amines such as dicyclohexylamine, dibutylamine oramines containing one cyclohexyl group and one alkyl group, or onebenzyl group and one alkyl group, such as ethylcyclohexylamine,ethylbenzylarnine, etc.

Other suitable compounds are exemplified by Other somewhat similarsecondary amines are those of the composition as described in U. S.Patent No. 2,375,659, dated May 8, 1945, to Jones et al. In the aboveformula R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other amines can be obtained from products which are sold in the openmarket, such as may be obtained by alkylation of cyclohexylmethylamineor the alkylation ofsirnilar primary amines, or for that matter, aminesof the kind described in U. S. Patent No. 2,482,546, dated September 20,1949, to Kaszuba, provided there is no negative group or halogenattached to. the phenolic nucleus. oxyethylamine,gamma-phenoxypropylamine, beta-phen oxy-alpha-methylethylamine, andbeta-phenoxypropylamlne.

Examples includesthe followingi beta-phen- Other suitable amines are thekind described in British.

Patent No, 456,517 and may be illustrated by The secondary categoryrepresents secondary amines which are hydroxylated monoamines. These maybe illustrated by diethanolamine, 'methylethanolamine, dipropanolamine,dibutanolamine and ethylpropanolamine. Suitable primary amines which canbe so converted mto secondary amines include butylamine, amylamine,hexylamine, higher molecular weight amines derived from fatty acids,cyclohexylamine, benzylamine, furfurylamme,

etc. 1

- droxylmethyl)-aminoethane. amines is illustrated by4-amino-4-methyl-2-pentanol.

Other suitable amines include 2'-amino-1'-butanol,2=

amino-Z-methyl-l-propanoLs.1 Z-amino-Z-methyl,1,3-prop-' anediol,2-amino-2-ethyl-1,3-propanedio1, and tris-(hy- Other suitable compoundsare the following:

olnroolHroorm I NH c,moclmoczmocluu 1100,11, olmocmomouoowrn)oHoHoHOC2H4 (OHaOCHsCHaQCHaCHrOOHsCHr) (ornocmornomcrnomom HOC2H|(ornocmomcmcmomom p NH HOCaHA or comparable compotinds having twohydroxylated (HO omomocmom0cmom) /NH H0 C2114 Other examples of suitableamines include alphamethylbenzylamine and m-onoethanolamine; also aminesobtained by treating cyclohexylmethylamine with one mole of anoxyalkylating agent as. previously described;beta-ethylhexylbutanolamine, diglycerylamine, etc. Another type of aminewhich is of particular interest because it includes a very definitehydrophile group includes sugar amines such as glucamine', galactamineand fructamine, such as N-hydroxyethylfructamine.

Other suitable'arnines may be illustrated by HO.CH2.

See also, corresponding hydroxylated amines which can be obtained fromrosin or similar raw materials and described in U. S. Patent No-2,510,063, dated June, 1950, to Bried.. Still other examples areillustrated by treatment of certain secondary amines, such as thefollowing, with ,a-mole ofan oxyalkylating agentas de-,

Another example.- of such 13 it is dilficult to actually depict thefinal product of the cogeneric mixture except in terms of theprocessitself.

The herein described amine-modified resins are obtained fromformaldehyde or in some instances glyoxal and resins of the kinddescribed in Part 1 preceding, in combination with secondary amines.Generally speaking in the preparation of conventional amine-modifiedresins the object is to obtain a heat-convertible compound or resin orat least heat convertible in presence of added formaldehyde. See, forexample, U. S. Patent No. 2,031,- 557 to Bruson. Since the condensationproducts obtained in the present invention are not heat-convertible andsince temperature up to 150 C. or thereabouts may be employed, it isobvious that the procedure becomes comparatively simple. Indeed,perhaps, no description is necessary over and above what has beenpreviously, in light of subsequent examples. However, for purpose ofclarity the following details are included.

A convenient piece of equipment for preparation of these cogenericmixtures is a resin pot of the kind described in aforementioned U. S.Patent No. 2,499,368. In most instances the resin selected is not apt tobe a fusible liquid, but is apt to be a solid even at highertemperatures, than at usual or ordinary. room temperature. Thus, I havefound it convenient to use a solvent and particularly one which can beremoved readily at a comparatively moderate temperature, for instance at150 C. or thereabouts. A suitable solvent is usually benzene, xylene ora comparable petroleum hydrocarbon or a mixture of such or similarsolvents. The reaction can be conducted in such a way that the initialreaction, and perhaps the bulk of the reaction, takes placein apolyphase system. However, if desirable, one can use an oxygenatedsolvent such as a low-boiling alcohol, including ethyl alcohol, methylalcohol, etc. Higher alcohols can be used or one can use a comparativelynon-volatile solvent such as dioxane or the diethylether ofethyleneglycol. One can also use a mixture of benzene or xylene and suchoxygenated solvents. Note that the use of such oxygenated solvent is notrequired in the sense thatit is not necessary to use an initial resinwhich is soluble only in an oxygenated solvent of the kind noted, and itis not necessary to have a single phase system for reaction.

Needless to say, the resins used are tetrafunctional. They could becombined with one mole of an appropriate amine or with 2 moles or with 3moles or with 4 moles. If combined with one mole, or with 2 moles of anappropriate amine there is no advantage in using thepreviously-described resins over the conventional resins derived fromdifunctional phenols only. The real advantage is the ability to combineat least 3 and more particularly 4 moles of amine with one mole of aresin having a total of 3 to 6 phenolic nuclei. For this reason thehereto appended claims specifically limit my invention to suchcombinations where at least 3 moles of appropriate amine is combinedwith 1 phenolic resin.

In the preparation of resin condensates the aldehydes used areformaldehyde and glyoxal. The use of glyoxal is limited to suchcompounds wherein insolubility does not occur. Needless to say, whenglyoxal is used to obtain substantially the same effect, the molar ratiois cut in two. In'the claims reference is made to formaldehyde as such,but obviously where glyoxal can be substituted such products would bewithin the. boundaries of the invention.

Although the condensation reaction can be conducted without the use of asolvent, in fact, it can be conducted using formaldehyde in highconcentrations or even the anhydrous equivalent, it is preferred to usethe 37% solution and also to use a solvent.

I have found no ditficulty in promoting the condensation reactionalthough at times it is desirable to add some solvent having a commonsolvent effect. Thus an oxygenated solvent may or may not be employed.Such solvent may be employed in combination with a hydrocarbon Solventsuch as xylene. However, if the reaction mass is going to be subjectedto some further reaction where the solvent may be objectionable as inthe case of ethyl or hexyl alcohol, and if there is to be subsequentoxyalkylation, then, obviously, the alcohols should not be used or elseit should be removed. The fact that an oxygenated solvent need notbe-employed, of course, is an advantage for reasons stated.

Another factor, as far as the selection of solvent goes,

is whether or not the cogeneric mixture obtained at the end-of thereaction is to be usedv as such 'or in the salt form. The cogenericmixtures obtained are apt to bev solids or thick viscous liquids inwhich there is someare invariably dark and'particularly reddish or darkred in color.

In some instances condensates have been prepared using a formaldehyde inone case and glyoxal in the other. Due to the difunctional property ofglyoxal the condensate frequently is harder and at times may even beinsoluble.

Indeed, depending on the resin selected and the amine selected thecondensate product or reaction mass on a solvent-free basis is apt to beharder than the original resin itself. This is particularly true whenall the amino hydrogen atoms present in the amine have entered into reaction, as in the case of a polyamine.

The products obtained, depending on the reactants selected, may bewater-insolublqor water-dispersible, or water-soluble, or close'to beingWater-soluble. Water solubility is enhanced, of course, by making asolution in the acidified vehicle such as a dilute solution, forinstance, a 5% solution of hydrochloric acid, acetic acid, hydroxyaceticacid, etc. One also may convert the finished product into salts bysimply adding a stoichiometric amount of any selected acid and removingany water present by refluxing with benzene or the like. In fact, theselection of the solvent employed may depend in part whether or not theproduct at the completion of the reaction is to be converted into a saltform.

It so happens as will be pointed out that frequently it is convenient toeliminate all solvent using a temperature of not over 150 C. andemploying vacuum if required. This applies, of course, only to thosecircumstances where it is desirable or necessary to remove the solvent.Petroleum solvents, aromatic solvents, etc., can

be used. The selection of solvent, such as benzene, xylene, or the like,depends primarily on cost, i. e., the use, of the most economicalsolvent and also on three other factors, two of which have beenmentioned previously; (a) is the solvent to remain in the reaction masswithout removal); (b) is the reaction mass to be subjected to furtherreaction in which the solvent, for instance, an alcohol, either lowboiling or high boiling, might interfere as in the case ofoxyalkylation?; and the third factor is this; (0) is an eifort to bemade to purify the reaction mass by the usual procedure as, for example,a water-wash to remove any unreacted low molal soluble amine if employedand present after reaction? Such procedures are well known,

and needless to say, certain solvents are more suitable than others.Everything else being equal, I have found xylene the most satisfactorysolvent.

I have found no advantage in using a low temperature, approximately roomtemperature, at the start of the reaction although this is sometimesdone purely as a matter of convenience. Indeed, using formaldehyde Ihave usually done nothing more than prepare the reaction mixture, add asuitable amount of xylene, and reflux for approximately 1 /2 to 6 /2hours at temperatures varying, as the case may be, from to C. Where theamine has a comparatively low basicity I have sometimes added a smallamount or approximately 1% of sodium methylate.

However, usinga xylene-benzene mixture, for instance, approximately 17parts. of benzene and 35 parts of xylene, and a phase-separating trap toeliminate water I have found that I could employ temperatures between 90and 100 -C., and eliminate the water of condensation by refluxing atthis temperature. However, I have found no particular advantage in usingthis intermediate temperature .over and above the high temperaturepreviously noted. I

The only bisphenol commercially available at quantity prices isbisphenol A. Thefour most readily available difunctional phenols havingalkyl groups of at least four carbon-atoms or more are: p-tertiary-amylphenol, p-tertiary-butyl phenol, octyl phenol and nonyl phenol. Thecheapest aldehyde and most suitable aldehyde is formaldehyde. 7 For thisreason the description of the con densation reaction has been limited tothese products which best serve as raw material in actual commercialmanufacture. Thus, the resins employed in the subsequent examples andtables are 1a, 18a, 19a and-20a. The latter was made from bisphenol B.

Generally speaking, the preference has beento, prepare condensates whichhad substantialhydrophile properties.

probably polymers may form. This may apply also a. symmetricallysubstituted polyamine such as ,di(hy- This usually means the use ofhydroxylated amines or polyamines. Those commercially availableand'particularly suitable include: diethanolamine, .diisopropanolamine,dibutanolamine and the polyamines whieh have been reacted withapproximately 2 mols of an alkylene oxide such as ethylene oxide. Suchcompounds include among otherssymmetrical di(hydroxyethyl) ethylenediamine, symmetrical di(hydroxyethyl) diethylene triami ne, symmetricaldi(hydroxypropyl) ethylene diamine, symmetrical di(hydroxybutyl)ethylene diamine and the com parable products derived from1,2-diaminopropar1e or-1, 3- diaminopropane. From a practical standpointmostreadily available amines include diethanolamine, diisopropanolamine,symmetrical di(hydroxyethyl). ethylene diamine, morpholine, etc. Usingdiamines, and especially a polyamine having a single reactivesecondary-amino group" such as the hydroxyethyl derivativeofdimethylamino propylamine obtained by the reaction of one incl ofethylene oxide and one mol of dimethylamino propylamine. yieldscondensates, which are particularly suitable for the present purpose.Another particularlysuitable amineis alpha-methylbenzylmonoethanolamine.

-It isnot necessary to point out that in the condensation reaction onemay obtain condensates which in all likelihood are monomers particularlywhen derived from a monoamino reactant such as diethanolamine ordiisopropanolamine. On the other-hand when derived from diamines inwhich there are two secondary aminogroups available for reactionobviously more complex forms and droxyethyl) diethylenetriamine ortriethylenetetramine or symmetrical di(hydroxyethyl)3,3-iminobispropylamine.

In making a large variety of condensates I employed conventional glasspots with appropriate heating jackets, condensers, and stirrers, etc.These glass pots had a capacity of approximately 5 liters. The procedureemployed is illustrated by the example immediately followmg:

Example 1b 954 grams of resin identified as 1a, was dissolved inapproximately 422 grams of xylene. To this was added 420.6 grams ofdiethanolamine. Aftenmixing at room temperature 3245 grams of 37%formaldehyde was added slowly and the temperature raised over a periodof time to approximately 150 C. and the mixture was allowed to refluxfor about 2 to 3 hours. During this period of time water of solution orwater of reactionwas withdrawn so that the mixture continued to refluxto 148 for another hour. In some instances some xylene was withdrawn andsome benzene added to hold the temperature in the approximate to 150range. Ac-

tually, the completion of condensation can be determined readily bycontinuing until no more water can be separated by means of aconventional phaseseparating trap. In thefinal product xlyene wasreturned to the mass if required or enough of the solvent was distilledout so that-the solvent remaining behind was the same as originallyadded. This was purely for a matter of convenience in order that themixture as completed contained the same amount of solvent as when itstarted.

In each instancea small amount of sample was heated to eliminate thexylene or other solvent. The resultant product was usually hardorsometimes tacky rather than hard and the color varied from reddish blackto almost black. In some instances the condensate was amber or darkbrown rather than reddish. The product so obtained could be bleachedwith the filtering chars or filtering earths. For most purposes, andparticularly when used subsequently as chemical reactant, there is noad.- vantagein suchbleaching. In such instancesgwhere there was atendency to form insoluble or semi-rubbery masses, there is someadvantage in using an oxygen-containing solvent such as the dimethylether of diethylene, glycol. Such solvent was used to replace the thirdor fourth of. the xylene or benzene.

Similar products were prepared as indicated in thefollowing tables:

TABLE III NorE .jln the above table 11A is used todesignatediethanolamine; BB is used to dash;- nate diisopropanolamine; QC isusedto, designate, alpha methylbenzylmonoethanolamine;

lsused to designate hydroxyethyl dimethylamino propylamine obtained byreaction betweenl mole of ethyleneoxide and 1 moleof dimcthylamtnopropylamine.

TABLE .IV

, priate' fashion.

Reaction data. Molalra Ratio 1:10 of- Water water Ex. N0. reactant out,out to Theo;

resin: grams aldehy. Max. Time pe- Char. of solventmolec. amine presenttemp. riod' Color of product free condensate weight aldehydepet-structural unit 1:4:4 270.5 0.92 148 2% Dk. amber Hard britt1e...1,422. 1:424 272. 4 0.95 146 2% Dk. purple do 1, 356 1:4:4 269. 5 0.91149 2% Dk. amber 1, 481 1:4:4 268 0.89. 149 3 Elk. amber 1, 641 1:4:4273 0.96 144 2% Dk. amber--- 1, 534 1:4:4 271. 7 -94 146 2% do 1,4681:4:4 268. 8 0.90 148 3. 0 1, 593 1:414 269. 0. 91 145 3 Amber blk 1,763 1:424 267. 3 0.88 147 2% Dk. amber 1, 6631 1:424. 268.7 0.90 147 2%Amber--- 1, 597 1:4:4 271 0.93. 145 3 Dk. amber; 1, 722'v 1:4:4 265. 20.85; 1 144. 3% Elk. brown--- 1, 882 1:4:4 266. 6 0.87 147 2% Very dk.brown. 1, 539 1:4:4 270. 5 0.92 149 2% Dk. amber 1, 473 1:4:4 267.30.88. 143 2% Elk. amber 1,598 1:4:4 264. 5 0.84 146 2% Dk. amber 1, 7581:412 322 0. 68 144 1% Dk. brown 1, 423 1:412 325 0.75 142 1% d0 1, 468'lystsuch as diamyl naphthalene sulf'onic'v acid together" with thesolvent. Formaldehyde can" be added iniappro- When resinification iscomplete and water of solution or water of reaction has been withdrawnby means of a phaseseparating trap the reaction mass can be cooled, andthe selected amine such'as diisopropanolamine can be added after havingpreviously added sufficient caustic soda to neutralize the sulfonicacid.. Form.

aldehyde can then beadded and the second onev of. the.

thecombinations possible inv complexity of' the structure of variouscondensates.

PART '4 As to the. use of. conventional demulsifying agents; referenceis made to U. S. Patent No. 2,626,929; datedi January 7, 1953, to DeGroote, and particularly to Part 3. Everything .that appearsthereiirapplies with equal force and effect to the instant process,noting only that Where reference is made to Example 1% in said textbeginning in column and ending in column 18, reference should be.toExamplelb, herein'described. 1

Having. thus described my invention, what I claim. as new and desire. tosecure. by Letters Patent is:

1. The process of breaking-petroleum emulsions, of thewater-'in-oiL-type characterized by sub-jecting'the emulsiontoademulsifying'agent including asynthetic hydrophile' product obtainedby the process of condensing. (a) an oxyalkylation-susceptible; fusible;organic solvent-soluble, watereinsoluble, low-stage phenol-aldehyderesin having an averagezmolecular' weight corresponding to at least 3and not over 6 phenolic nucleiper resin molecule; said resinlbeingsderived.by reaction b'etweenan aldehyde-hav-.

Thus; one can use a".

ing'not over 8 carbon atoms and.reactive.towardsitwo. classes ofphenols; one being (A) a phenolof the formula in which R- is analiphatic hydrocarbon radical having atleast 4 and notmore than-24carbon atomszand'suo stituted inthe 2,4,6position; the'other. being(B) a tetra:- functional bisphenol; the ratio of 1 the two classes. ofphenols employed being so as tocontribute one bisphenol residue perresinmolecule; (b) apbasichydroxylated.sec-

46, ondary amine free fromanyprimary amino. radical and having not morethan 32 carbon1atoms.in any groupjat tached to any aminonitrogenradicaland reactive towards. formaldehyde; (0) formaldehyde; said condensationreaction being conducted'at a'temperaturesufiiciently high-.toeliminatewater and belowthe pyrolytic point of.'the.reactantsand-resultants of reaction; with the proviso that the. ratio ofreactantsbe approximately within the. range of 1,3, and 3to 1,4 and 4respectively; and'with the added proviso that-the resinous condensationproduct resulting from the process beh'eat stabl'e. p 1

2. The process of breakingpetroleum emulsions. of 'the Water-in-oil typecharacterizedby'subjecting the emulsion toa demulsifyingagent includinga synthetic hydrophile product obtainedb-y the process of condensing,(a), an oxyalkylation-susceptible, fusible; organic solvent-soluble,water-insoluble, low-stage phenol-aldehyde resin having an averagemolecular weight. corresponding to at least 3 and not over 6 phenolicnuclei per resin molecule; said resin being derived by reaction betweenan aldehyde having not over 8 carbon atomsxand reactive towards twoclasses: ofv phenols, one:heing;(A);aphenol:ofi the formula? residue perresin molecule; (17) a basic hydroxylated sec: ondarymonoamine having.not more than 32 carbon atoms.

inany group attachedto the amino nitrogen atom and reactivetowards'formaldehyde; ('c) formaldehyde;"said" 49 condensation reactionbeing "conducted at a temperature sufliciently high to eliminate waterand below the pyrolytic point of the reactants and resultants ofreaction; with the proviso that the ratio of reactants be approximatelywithin the range of 1,3 and 3 to 1,4 and 4 respectively; and with thefinal proviso that the resinous condensation product resulting from theprocess be heat-stable.

3. The process of breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to a demulsifying agentincluding a synthetic hydrophile product obtained by the process ofcondensing (a) an oXyalkylation-susceptible, fusible, organicsolvent-soluble, water-insoluble, low-stage phenol-aldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being derived by reactionbetween an aldehyde having not over 8 carbon atoms and reactive towardstwo classes of phenols, one being (A) a .phenol of the formula in whichR is an aliphatic hydrocarbon radical having at least 4 and not morethan 24 carbon atoms and substituted in the 2,4,6 position; the otherbeing (B) a tetrafunctional bisphenol; the ratio of the two classes ofphenols employed being so as to contribute one bisphenol residue perresin molecule; (b) a basic hydroxylated secondary monoamine having notmore than 32 carbon atoms in any group attached to the amino nitrogenatom and reactive towards formaldehyde; formaldehyde; said condensationreaction being conducted at a temperature sutficiently high to eliminatewater and below the pyrolytic point of the reactants and resultants ofreaction; with the added proviso that the condensation reaction beconducted so as to produce a significant portion of the resultant inwhich each of the three reactants have contributed part of the ultimatemolecule; with the proviso that the ratio reactants be approximatelyWithin the range of 1,3 and 3 to 1,4 and 4 respectively; and with thefurther proviso that the resinous condensation product resulting fromthe process be heat-stable. v

4. The process of breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting'the emulsion to a demulsifying agentincluding a synthetic hydrophile product obtained by the process ofcondensing (a) an oxyalkylation-susceptible, fusible, organicsolventsoluble, water-insoluble, low-stage phenol-aldehyde resin havingan average molecular weight correspondingto at least 3 and not over 6phenolic nuclei per resin molecule; said resin being derived byreaction'between an aldehyde having not over 8 carbon atoms and reactivetowards two classes of phenols, one being (A) a phenol of the formula inwhich R is an aliphatic hydrocarbon radical having at least 4 and notmore than 24 carbon atoms and substituted in the 2,4,6 position; theother being (B) a tetrafunctional bisphenol; the ratio of the twoclasses of phenols employed being so as 'to contribute one bisphenolresidue per resin molecule; (b) a basic hydroxylated secondary monoaminehaving not more than 32 carbon atoms in any group attached to the aminonitrogen atom and reactive towards formaldehyde; (0) formaldehyde; saidcondensation reaction being conducted at a temperature sutficiently highto eliminate water and below the, pyrm lytic point of the reactants andresultants of reaction; with the proviso that the condensation reactionbe conducted so as to produce a significant portion of the re sultant inwhich eachof the three reactants have contributed part of the ultimatemolecule by virtue of a formaldehyde derived methylene bridge connectingthe amino nitrogen atom with a resin molecule; with the further provisothat the ratio of reactants be, approximately 1,4 and 4 respectively;andrwith the final proviso that the resinous condensation productresulting from the process be heat-stable.

5. The process of breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to a demulsifying agentincluding a synthetic hydrophile product obtained by the process ofcondensing (a) an oxyalkylation-susceptible, fusible, organicsolvent-soluble, water-insoluble, low-stage phenol-aldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being derived by reactionbetween an aldehyde having not over 8 carbon atoms and reactive towardstwo classes of phenols, one being (A) a phenol of the formula in which Ris an aliphatic hydrocarbon radical having at least 4 and not more than24 carbon atoms and substi-- tuted in the 2,4,6 position; the otherbeing (B) a tetrafunctional bisphenol; the ratio of the two classes ofphenols employed being so as to contribute one bisphenol residue perresin molecule; (b) a basic hydroxylated secondary monoamine having notmore than 32 carbon atoms in any group attached to the amino nitrogenatom and reactive toward formaldehyde; (0) formaldehyde; saidcondensation reaction being conducted at a temperature sufficiently highto eliminate Water and below the pyro lytic point of the reactants andresultants of reaction; with the proviso that the condensation reactionbe conducted so as to produce a significant portion of the resultant inwhich each of the three reactants have contributed part of the ultimatemoleculeby virtue of a formaldehyde derived methylene bridge connectingthe amino nitrogen atom with a resin molecule; with the further provisothat the ratio of reactants be approximately 1, 4 and 4 respectively;with the further proviso that said procedure involve the use of asolvent; and withthe final proviso thatthe resinous condensation productresulting from the process be heat-stable.

6. The process of breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to a demulsifying agentincluding a synthetic hydrophile product obtained by the process ofcondensing (a) an oxyalkylation-susceptible, fusible, organicsolvent-soluble, water-insoluble, low-stage phenolaldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being derived by reactionbetween formaldehyde and two classes of phenols, one being (A) a phenolof the formula in which R is an aliphatic hydrocarbon radical having atleast 4 and not more than 24 carbon atoms and substituted in the 2,4,6position; the other being (B) a tetrafunctional bisphenol; the ratio ofthe two classes of phenols employed being so as to contribute onebisphenol residue per resin molecule; (b) a basic hydroxylated secondarymonoamine having not more than 32 carbon atoms in any group attached tothe amino nitrogen atom and reactive towards formaldehyde; (0)formaldehyde; said condensation reaction being'conducted at atemperature sufliciently high to eliminate water and below the pyrolytic point of the reactants, and resultants of reaction;

21 with the proviso that the condensation reaction be conducted so as toproduce a significant portion of the -resultant in which each of thethree reactants have contributed part of the ultimate molecule by virtueof a formaldehyde derived methylene bridge connecting the amino nitrogenatom with a resin molecule; with the further proviso that the ratio ofreactants be approximately 1,4 and 4 respectively, with the furtherproviso that said procedure involve the use of a solvent; and with thefinal proviso that the resinous condensation resulting from the processbe heat-stable.

7. The process of breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to a demulsifying agentincluding a synthetic hydrophile product obtained by the process ofcondensing (a) an oxyalkylation-susceptible, fusible, organicsolvent-soluble, water-insoluble, low-stage phenolaldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being derived by reactionbetween formaldehyde and two classes of phenols, one being (A) a phenolof the formula product in which R is an aliphatic hydrocarbon radicalhaving at least 4 and not more than 14 carbon atoms and substituted inthe 2,4,6 position; the other being (B) a tetrafunctional bisphenol; theratio of the two classes of phenols employed being so as to contributeone bisphenol residue per resin molecule; (b) a basic hydroxylatedsecondary monoamine having not more than 32 carbon atoms in any groupattached to the amino nitrogen atom and reactive towards formaldehyde;(c) formaldehyde; said condensation reaction being conducted at atemperature sufliciently high to eliminate water and below the pyrolyticpoint of the reactants and resultants of reaction; with the proviso thatthe condensation reaction be conducted so as to produce a significantportion of the resultant in which each of the three reactants havecontributed part of the ultimate molecule by virtue of a formaldehydederived methylene bridge connecting the amino nitrogen atom with a resinmolecule; with the further proviso that the ratio of reactants beapproxi-' mately 1,4 and 4 respectively, with the further proviso thatsaid procedure involve the use of a solvent and with the final provisothat the resinous condensation product resulting from the process beheat-stable.

8. The process of breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to a demulsifying agentincluding a synthetic hydrophile product obtained by the process ofcondensing (a) an oxyalkylation-susceptible, fusible, organicsolvent-soluble, water-insoluble, low-stage phenolaldehyde resin havingan average molecular weight corresponding to at least 3 and not over 5phenolic nuclei per resin molecule; said resin being derived by reactionbetween formaldehyde and two classes of phenols, one being (A) a. phenolof the formula in which R is an aliphatic hydrocarbon radical having atleast 4 and not more than 14 carbon atoms and substituted in the 2,4,6position; the other being (B) a tetrafunctional bisphenol; the ratio ofthe two classes of phenols employed being so as to contribute onebisphenol residue per resin molecule; (b) a basic hydroxylated secondarymonoamine having not more than 32 carbon atoms in any group attached tothe amino nitrogen atom and reactive towards formaldehyde; (c)formaldehyde; said condensation reaction being conducted at atemperature sufliciently high to eliminate water and below the pyrolyticpoint of the reactants and resultants of reaction; with the proviso thatthe condensation reaction be conducted so as to produce a significantportion of the resultant in which each of the three reactants havecontributed part of the ultimate molecule by virtue of a formaldehydederived methylene bridge connecting the amino nitrogen atom with a resinmolecule; with the further proviso that the ratio of reactants beapproximately 1,4 and 4 respectively, with the further proviso that saidprocedure involve the use of a solvent and with the final proviso thatthe resinous condensation product resulting from the process beheat-stable.

9. The process of breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to a demulsifying agentincluding a synthetic hydrophile product obtained by the process ofcondensing (a) an oxyalkylation-susceptible, fusible, organicsolvent-soluble, water-insoluble, low-stage phenolaldehyde resin havingan average molecular weight corresponding to at least 3 and not over 5phenolic nuclei per resin molecule; said resin being derived by reactionbetween formaldehyde and two classes of phenols, one being (B) a phenolof the formula in which R is an aliphatic hydrocarbon radical having atleast 4 and not more than 14 carbon atoms and substituted in the 2,4,6position; the other being (B) a tetrafunctional bisphenol; the ratio ofthe two classes of phenols employed being so as to contribute onebisphenol residue per resin molecule; (b) a basic hydroxylated secondaryamine having at least two alkanol radicals which in turn have not over 8carbon atoms in each alkanol radical and reactive towards formaldehyde;(c) formaldehyde; said condensation reaction being conducted at atemperature sufficiently high to eliminate water and below the pyrolyticpoint of the reactants and resultants of reaction; with the proviso thatthe condensation reaction be conducted so as to produce a significantportion of the resultant in which each of the three reactants havecontributed part of the ultimate molecule by virtue of a formaldehydederived methylene bridge connecting the amino nitrogen atom with a resinmolecule; with the further proviso that the ratio of reactants beapproximately 1,4 and 4 respectively, with the further proviso that saidprocedure involve the use of a solvent and with the final proviso thatthe resinous condensation product resulting from the process beheatstable.

References Cited in the file of this patent UNITED STATES PATENTS

1. THE PROCESS OF BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPECHARACTERIZED BY SUBJECTING THE EMULSION TO A DEMULSIFYING AGENTINCLUDING A SYNTHETIC HYDROPHILE PRODUCT OBTAINED BY THE PROCESS OFCONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANICSOLVENT-SOLUBLE WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVINGAN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DERIVED BY REACTIONBETWEEN AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARDSTWO CLASSES OF PHENOLS, ONE BEING (A) APHENOL OF THE FORMULA